A methodology of general validity to prepare epitaxial nanocomposite films is reported based on the use of colloidal solutions containing different crystalline preformed oxide nanoparticles (ex-situ nanocomposites). The trifluoroacetate (TFA) metal-organic chemical solution deposition route is used with alcoholic solvents to grow epitaxial YBa 2 Cu 3 O 7 (YBCO) films. For that reason stabilizing oxide nanoparticles in polar solvents is a challenging goal. We have used scalable nanoparticle synthetic methodologies such as thermal and microwave-assisted solvothermal techniques to prepare CeO 2 and ZrO 2 nanoparticles. We show that stable and homogeneous colloidal solutions with these nanoparticles can be reached using benzyl alcohol, triethyleneglycol, nonanoic acid, trifluoroacetic acid or decanoic acid as protecting ligands, thereby allowing subsequent mixing with alcoholic TFA solutions. An elaborate YBCO film growth analysis on these nanocomposites allows the identification of the different relevant growth phenomena, e.g. nanoparticle pushing towards the film surface, nanoparticle reactivity, coarsening and nanoparticle accumulation at the substrate interface. Upon mitigation of these effects, YBCO nanocomposite films with high self-field critical currents (J c 3-4 MA/cm 2 at 77 K) were reached, indicating no current limitation effects associated to epitaxy perturbation, while smoothed magnetic field dependences of the critical currents at high magnetic fields and decreased effective anisotropic pinning behavior confirms the effectiveness of the novel developed approach to enhance vortex pinning. In conclusion, a novel low cost solution-derived route to high current nanocomposite superconducting films and coated conductors has been developed with very promising features.

Although high temperature superconductors are promising for power applications, the production of low‐cost coated conductors with high current densities—at high magnetic fields—remains challenging. A superior superconducting YBa2Cu3O7–δ nanocomposite is fabricated via chemical solution deposition (CSD) using preformed nanocrystals (NCs). Preformed, colloidally stable ZrO2 NCs are added to the trifluoroacetic acid based precursor solution and the NCs' stability is confirmed up to 50 mol% for at least 2.5 months. These NCs tend to disrupt the epitaxial growth of YBa2Cu3O7–δ, unless a thin seed layer is applied. A 10 mol% ZrO2 NC addition proved to be optimal, yielding a critical current density JC of 5 MA cm−2 at 77 K in self‐field. Importantly, this new approach results in a smaller magnetic field decay of JC(H//c) for the nanocomposite compared to a pristine film. Furthermore, microstructural analysis of the YBa2Cu3O7–δ nanocomposite films reveals that different strain generation mechanisms may occur compared to the spontaneous segregation approach. Yet, the generated nanostrain in the YBa2Cu3O7–δ nanocomposite results in an improvement of the superconducting properties similar to the spontaneous segregation approach. This new approach, using preformed NCs in CSD coatings, can be of great potential for high magnetic field applications.

Achieving low cost, safe, reproducible and high performance superconducting thin films of YBa2Cu3O7-δ is essential to bring this material to the energy market. Here, we report on the chemical solution deposition of YBa2Cu3O7-δ nanocomposites from environmentally benign precursors with a low-fluorine content. Preformed ZrO2 nanocrystals (3.5 nm) were stabilized in a methanolic precursor solution via two strategies: charge stabilization and steric stabilization. Counter-intuitively, charge stabilization did not result in high quality superconducting layers, while the steric stabilization resulted in highly reproducible nanocomposite thin films with a self-field Jc of 4-5 MA cm -² (77 K) and a much smaller decay of Jc with magnetic field compared to YBa2Cu3O7-δ without nanocrystals. In addition, these nanocomposite films show a strong pinning force enhancement and a reduced Jc anisotropy compared to undoped YBa2Cu3O7-δ films. Given the relationship between the nanocrystal surface chemistry and final nanocomposite performance, we expect these results to be also relevant for other nanocomposite research.-2 -

This work presents a novel anticounterfeiting strategy based on a material changing its emission color in response to a change in the excitation sources—where a single ultraviolet (UV) or near‐infrared (NIR) light source are employed or simultaneously using two excitation sources (xenon lamp and NIR laser). Following this approach, various combinations of lanthanide (Ln3+)‐doped LiLuF4/LiYF4 core/shell nanoparticles are prepared, providing a promising route to design flexible nanomaterials, as well as already a small library of luminescent materials, which change color when varying the excitation source (UV, NIR or both UV and NIR). Aside from excitation source‐dependent color change, these materials additionally show excitation‐source power‐dependent color change. This work exploits the possibility of developing a new class of multimode anticounterfeit nanomaterials, with excellent performance, which would be almost impossible to mimic or replicate, providing a very high level of security.

Lanthanide-doped luminescent nanoparticles are an appealing system for nanothermometry with biomedical applications due to their sensitivity, reliability and minimally invasive thermal sensing properties. Here, we propose four unique hybrid organic-inorganic materials prepared by combining β-NaGdF4 and PMOs (Periodic Mesoporous Organosilica) or mSiO2 (mesoporous silica). PMO/mSiO2 materials are excellent candidates for biological/biomedical applications as they show high biocompatibility with the human body. On the other hand, the β-NaGdF4 matrix is an excellent host for doping lanthanide ions, even at very low concentrations with yet very efficient luminescence properties. We propose a new type of Er 3+ -Yb 3+ upconversion luminescence nanothermometers operating both in the visible and near infrared regime. Both spectral ranges permit promising thermometry performance even in aqueous environment. It is additionally confirmed that these hybrid materials are non-toxic to cells, which makes them very promising candidates for real biomedical thermometry applications. In several of these materials the presence of additional voids leaves space for future theranostic or combined thermometry and drug delivery applications in the hybrid nanostructures.

1 AbstractLigand exchange is a crucial step between nanocrystal synthesis and nanocrystal application. Although colloidal stability and ligand exchange in nonpolar media is readily established, the exchange of native, hydrophobic ligands with polar ligands is less systematic. In this paper, we present a versatile ligand exchange strategy for the phase transfer of carboxylic acid capped HfO 2 and ZrO 2 nanocrystals to various polar solvents, based on small amino acids as the incoming ligand. To gain insight in the fundamental mechanism of the exchange, we study this system with a combination of FTIR, zeta potential measurements and solution 1 H NMR techniques. The detection of surface-associated, small ligands with solution NMR proves challenging in this respect. Tightly bound amino acids are undetectable but their existence can be proven through displacement with other ligands in titration experiments. Alternatively, we find that methyl moieties belonging to bound species can circumvent these limitations because of their more favorable relaxation properties as a result of internal mobility.

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are a new type of support for grafting lanthanide ions (Ln3+), which can be employed as ratiometric luminescent thermometers. In this work we have shown that COFs co‐grafted with lanthanide ions (Eu3+, Tb3+) and Cu2+ (or potentially other d‐metals) can synchronously be employed both as a nanothermometer and catalyst during a chemical reaction. The performance of the thermometer could be tuned by changing the grafted d‐metal and solvent environment. As a proof of principle, the Glaser coupling reaction was investigated. We show that temperature can be precisely measured during the course of the catalytic reaction using luminescence thermometry. This concept could be potentially easily extended to other catalytic reactions by grafting other d‐metal ions on the Ln@COF platform.

Inherent substrate selectivity is reported for the thermal RuO4 (ToRuS)/H2 gas atomic layer deposition (ALD) process on H-terminated Si (Si–H) versus SiO2. In situ spectroscopic ellipsometry (SE) detected Ru growth from the first cycle on blanket Si–H, whereas on blanket SiO2, 60 cycles were needed to detect growth. Area-selective growth was evaluated on a patterned substrate with 1–10 μm wide Si–H lines separated by 10 μm wide SiO2 regions. Ex situ planar scanning electron microscopy and cross-sectional high-resolution transmission electron microscopy measurements showed that a smooth, continuous Ru film of 4.5 nm could be deposited on Si–H, with no Ru detected on SiO2. The proposed mechanism behind the inherent substrate selectivity is the oxidation of the Si–H surface by RuO4, which was confirmed by in vacuo X-ray photoelectron spectroscopy (XPS) experiments. A methodology to enhance the nucleation of the RuO4/H2 gas process on oxide substrates is also reported. In situ SE and in vacuo XPS experiments show that the nucleation delay on SiO2 can be completely removed by exposing the surface to trimethylaluminum (TMA) just before the start of the ALD process. We found evidence that the TMA pulse makes the oxide surface reactive toward RuO4, by introduction of surface methyl groups, which can be combusted by RuO4. As TMA is known to be reactive toward many oxide substrates, this methodology presents a way to achieve Ru metallization of virtually any surface. Therefore, one can either (i) use the RuO4/H2 gas process to coat nonoxidized surfaces selectively with Ru or (ii) use TMA-priming by which one can bypass the selectivity and coat a wide variety of surfaces nonselectively with Ru.